CN1099052A - The black dye mixer of fiber-reactive azo dyes and application thereof - Google Patents

The black dye mixer of fiber-reactive azo dyes and application thereof Download PDF

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CN1099052A
CN1099052A CN93120600A CN93120600A CN1099052A CN 1099052 A CN1099052 A CN 1099052A CN 93120600 A CN93120600 A CN 93120600A CN 93120600 A CN93120600 A CN 93120600A CN 1099052 A CN1099052 A CN 1099052A
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dye mixture
structural formula
dyestuff
phenyl
sulfuric acid
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K·胡松格
W·H·鲁斯
K·克里格
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Hoechst AG
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Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C09B67/0046—Mixtures of two or more azo dyes
    • C09B67/0047—Mixtures of two or more reactive azo dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C09B67/0046—Mixtures of two or more azo dyes
    • C09B67/0047—Mixtures of two or more reactive azo dyes
    • C09B67/005—Mixtures of two or more reactive azo dyes all the reactive groups being not directly attached to a heterocyclic system
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/10—Material containing basic nitrogen containing amide groups using reactive dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Coloring (AREA)

Abstract

The invention discloses a kind of dye mixture, this dye mixture contains one or more disazo dyess that meet structural formula (1) and one or more meet the monoazo-dyes (its structural formula is as shown in specification sheets) of structural formula (2).

Description

The black dye mixer of fiber-reactive azo dyes and application thereof
The present invention relates to the field of fibre-reactive dyes.
The invention provides some dye mixtures, this mixture comprises that one or more (for example a kind of, two or three) meet the disazo dyes of structural formula (1), and one or more (for example a kind of, two or three) meet the monoazo-dyes of structural formula (2).Wherein, the content that meets the disazo dyes of structural formula (1) be 50-95%(by weight), and the content that meets the monoazo-dyes of structural formula (2) be 5-50%(by weight).
The meaning of each code name is as follows in structural formula (1) and (2):
R 1Be hydrogen, methyl, ethyl, methoxyl group, oxyethyl group, sulfonic group or carboxyl, preferred methoxyl group and hydrogen, more preferably hydrogen;
R 2Be hydrogen, methyl, ethyl, methoxyl group, oxyethyl group, sulfonic group or carboxyl, preferred hydrogen;
R 3Be hydrogen, methyl, ethyl, methoxyl group, oxyethyl group, sulfonic group or carboxyl, preferred methoxyl group and hydrogen, more preferably hydrogen;
R 4Be hydrogen, methyl, ethyl, methoxyl group, oxyethyl group, sulfonic group or carboxyl, preferred hydrogen;
R 5Be hydrogen, methyl, ethyl, methoxyl group, oxyethyl group, sulfonic group or carboxyl, preferred methoxyl group and hydrogen, more preferably hydrogen;
R 6Be hydrogen, methyl, ethyl, methoxyl group, oxyethyl group, sulfonic group or carboxyl, preferred hydrogen;
Y is respectively vinyl, β-chloroethyl, β-thiosulfuric acid ethyl or β-sulfuric acid ethyl separately;
M is hydrogen or basic metal, as lithium, sodium and potassium;
Preferably and azo-group be between position or contraposition, be connected on the phenyl ring-SO 2-Y base.
Some code name can have identical or different meaning in structural formula (1) and (2) in the scope of its definition.
This dye mixture can comprise in addition that content is at most 10%, preferably is at most 5%(by weight), the yellow or red coloured light dyestuff of adjusting.The known dyestuff of this class is for example to meet structural formula (a) and (b), (c) and monoazo-dyes (d),
Figure 931206006_IMG6
Figure 931206006_IMG7
In the formula,
D is 3-(β-sulfuric acid ethyl sulphonyl) phenyl, 4-(β-sulfuric acid ethyl sulphonyl) phenyl, 3-ethene sulfonyl-phenyl, 4-ethene sulfonyl-phenyl, 2-methoxyl group-5-(β-sulfuric acid ethyl sulphonyl) phenyl or 2-methoxyl group-5-ethene sulfonyl-phenyl,
The M definition is the same,
R 10Be vinyl, the Bian acyl group, 4 that on phenyl ring, is replaced by methyl or methoxy; 6-dicyan amino-1; 3; 5-triazine-2-base, 4-cyanogen amino-6-(sulfonic acid phenylamino)-1,3,5-triazines-2-base, 4-(N-morpholino)-6-(sulfonic acid phenylamino)-1; 3; 5-triazine-2-base or 4-(N-morpholino)-6-(sulfonic acid phenylamino)-1,3,5-triazines-2-base
R 11Be vinyl, the formamyl, 4 that on phenyl ring, is replaced by methyl or methoxy; 6-dicyan amino-1; 3,5-triazine-2-base, 4-cyanogen amino-6-(sulfonic acid phenylamino)-1,3; 5-triazine-2-base, 4-(N-morpholino)-6-(sulfonic acid phenylamino)-1; 3,5-triazine-2-base or 4-(N-morpholino)-6-(sulfonic acid phenylamino)-1,3; 5-triazine-2-base
R 12Be methyl or carboxyl,
R 13Be sulfonic group, β-chloroethyl alkylsulfonyl or β-sulfuric acid ethylsulfonyl,
R 14Be hydrogen or methyl,
R 15Be hydrogen, cyano group, formamyl, carboxyl or sulfonic acid methyl,
R 16Be methyl, ethyl or β-sulfonic acid ethyl.
In the document, the dyestuff of structural formula (1) and (2) is well-known, and for example United States Patent (USP) 2,657,205, Japanese Patent disclose clear and-disazo dyes of structural formula (1) disclosed in 58-160 362, United States Patent (USP) 4,257,770 and the reference quoted thereof.The monoazo-dyes of structural formula (2) is at United States Patent (USP) 5,093, also done introduction in 483.
The dye mixture of preferred construction formula (1) and (2) comprise content be 60-80%(by weight) the disazo dyes of structural formula (1) and content be 20-40%(by weight) the monoazo-dyes of structural formula (2).
Sulfonic group is meant formula-SO 3M base, carboxyl are meant-the COOM base that sulfate is meant formula-OSO 3The M base, the thiosulfuric acid base is meant formula-S-SO 3The M base.
The dyestuff of structural formula (1) and structural formula (2) when especially these dyestuffs have identical chromophoric group, can have the different fiber reactivity base-SO of structure in the range of definition of Y 2-Y.Particularly this dye mixture can contain identical chromophoric group and meets the dyestuff of formula (1) and/or contain the dyestuff that identical chromophoric group meets formula (2), fiber reactivity base-SO wherein 2-Y, a part is the ethene alkylsulfonyl, a part is β-chloroethyl alkylsulfonyl or β-thiosulfuric acid base ethylsulfonyl or preferred β-sulfuric acid ethylsulfonyl.If contain the relevant dyestuff composition of ethene alkylsulfonyl dye form in this dye mixture; then based on relevant dye chromophore, relevant ethene alkylsulfonyl dyestuff can be up to about 30 moles of % with the ratio of relevant β-chloroethyl alkylsulfonyl or β-thiosulfuric acid base ethylsulfonyl or β-sulfuric acid ethylsulfonyl dyestuff.
Preferred dye mixture is that the mol ratio of therein ethylene alkylsulfonyl and β-sulfuric acid ethylsulfonyl dyestuff is 5: 95-30: between 70.
Preferred another kind of dye mixture meets the monoazo-dyes of structural formula (11) for the disazo dyes that one or more meet structural formula (10) with one or more,
In the formula, the definition of M is the same, D 1, D 2And D 3Be respectively 3-vinyl sulfonyl-phenyl, 4-vinyl sulfonyl-phenyl, 3-(β-sulfuric acid ethyl sulphonyl separately) phenyl or 4-(β-sulfuric acid ethyl sulphonyl) phenyl; if this dye mixture contains ethene alkylsulfonyl and β-sulfuric acid ethylsulfonyl simultaneously, then the mol ratio of ethene alkylsulfonyl part and β-sulfuric acid ethylsulfonyl part is 5: 95-30: between 70.
Preferred another kind of dye mixture meets the dyestuff of structural formula (11) for the dyestuff that one or more meet structural formula (10) with one or more, wherein, and D 1And D 2Be respectively 3-(β-sulfuric acid ethyl sulphonyl separately) phenyl, 4-(β-sulfuric acid ethyl sulphonyl) phenyl, 3-vinyl sulfonyl-phenyl or 4-vinyl sulfonyl-phenyl, and D 3Be 2-methoxyl group-5-(β-sulfuric acid ethyl sulphonyl) phenyl or 2-methoxyl group-5-ethene sulfonyl-phenyl; if this dye mixture contains ethene alkylsulfonyl and β-sulfuric acid ethylsulfonyl simultaneously, then the mol ratio of ethene alkylsulfonyl part and β-sulfuric acid ethylsulfonyl part is 5: 95-30: between 70.
Dye mixture of the present invention can be made into solid form or liquid state (dissolved) form.The dye mixture of solid form contains the especially usual electrolyte salt of using of fibre-reactive dyes of water-soluble dye usually, as sodium-chlor, Repone K, the usual auxiliary agent that uses in sodium sulfate and the commercially available dyestuff, for example can make pH value of aqueous solution reach buffer substance between the 3-7, such as sodium-acetate, Sodium Tetraborate, sodium bicarbonate, SODIUM PHOSPHATE, MONOBASIC and Sodium phosphate dibasic and a spot of siccative, if or this dye mixture system is liquid aqueous solution state (containing the usual thickening material that uses of printing paste), then contain usually and can make these liquid formulations keep stable material, for example mould inhibitor.
Generally speaking, this dye mixture system is the dye powder state, wherein contains 10-80%(by weight, is benchmark with the weight of dye powder or preparation) the colourless dilution electrolyte salt of strength criterionization.This dye powder can contain total amount in addition and be at most 5% above-mentioned buffer substance (weight with dye powder is benchmark).If dye mixture of the present invention is mixed with the aqueous solution, then the total content of this dyestuff in the aqueous solution is about 50%(by weight at the most), for example (by weight) between the 5-50%, the content of preferred above-mentioned Enthalpy of Electrolytes in Aqueous Solutions salt is lower than 10%(by weight, is benchmark with the weight of the aqueous solution).This aqueous solution (liquid preparation) generally can contain 5%(at the most by weight) above-mentioned buffer substance, preferred 2%(is by weight).
Dye mixture of the present invention can make with the method for routine, for example in required ratio with various dyestuffs with mechanically mixing or utilize suitable diazonium composition and coupling mixture of ingredients, in a manner familiar to those skilled in the art, in required ratio, synthesize with usual diazotization reaction and the coupled reaction that adopts.A kind of scheme is the aqueous solution that for example prepares two kinds of coupling compositions (1-amino-8-naphthol-3,6-disulfonic acid and 2 hydroxy naphthalene-6-carboxylic acid), and as the aqueous solution of the aniline compound that meets structural formula (3a), (3b) and/or (4) of diazonium composition,
Figure 931206006_IMG9
In the formula, R 1, R 2, R 3, R 4, R 5, R 6The same with Y definition separately.By proper proportion in strong acid media with conventional method with above-mentioned aniline compound diazotization, then, be lower than at pH under 1.5 the condition 1-amino-8-naphthol-3,6-disulfonic acid and above-mentioned a kind of diazonium composition carry out coupled reaction.Under the condition of 3-6, monoazo-dyes product and another kind of diazonium composition carried out second time coupled reaction to generate disazo dyes at pH.Then, add the aqueous solution of 2 hydroxy naphthalene-6-carboxylic acid and another kind of diazonium composition, under the condition of 3-6, carry out coupled reaction meets structural formula (2) with generation monoazo-dyes at pH.The dye mixture that makes like this can adopt ordinary method for example to use electrolytic salt (as sodium-chlor, Repone K or lithium chloride) to saltout or spraying drying is separated it from solution.
Dye chromophore for example not only contains β-chloroethyl alkylsulfonyl or β-thiosulfuric acid ethylsulfonyl or β-sulfuric acid ethylsulfonyl but also contains ethene alkylsulfonyl dye mixture partly; not only can use method for preparing; and can utilize the suitable initial aniline of ethene alkylsulfonyl to be the dye mixture of β-chloroethyl or β-thiosulfuric acid ethyl or β-sulfuric acid ethyl and a certain amount of the required alkali reaction of part reaction with these bases by Y, make the ethylsulfonyl of described beta substitution be converted into the ethene alkylsulfonyl and make.This measure is that the method that the ethylsulfonyl with beta substitution known to adopting usually is converted into the ethene alkylsulfonyl realizes.
The application method and the fixing means of the fibre-reactive dyes that employing present technique field is repeatedly introduced; the filamentary material that contains hydroxyl and/or formamyl can be dyed the aterrimus tone with the structural formula (1) of novelty and the dye mixture of (2); have good color pile-on properties after this material is dyed, and loose dyestuff partly is easy to flush away.In addition, the gained product dyed thereby is easy to discharge.
Therefore; the present invention also provide should novelty dye mixture to the application of the filamentary material dyeing (comprising printing and dyeing) of hydroxyl and/or formamyl and utilize the dye mixture of the present invention this kind filamentary material is carried out painted method; promptly utilize the dye mixture of dissolved state of the present invention that this base material is dyeed, and by alkali or heating or the effect that has both concurrently with dyestuff fixing on fiber.
The material of hydroxyl can be natural or synthetic, for example cellulosic fibre material (comprising the material or its reconstituted product that are the paper shape) and polyvinyl alcohol.
Preferred cellulosic fibre material is the cotton product, yet also can be other vegetable fibre, such as flax fiber, hemp fibre, jute fibre and ramee; Other regenerated cellulose fibre such as staple fibre viscose and macrofiber viscose.
The material that contains formamyl is for example synthetic and natural polymeric amide and urethane, especially is hair, silk, leather, nylon-6 .6, nylon-6, nylon-11 and the nylon-4 of fibrous for example wool, other animal.
Dye mixture of the present invention normally adopts known fibre-reactive dyes application technique to be applied to the dyeing and the printing and dyeing of filamentary material.Because the dyestuff consistency height each other of dye mixture of the present invention, therefore, dye mixture of the present invention helps using dying in the method to the greatest extent.According to the method, for example adopt big bath raio, under temperature 40-105 ℃ with dye mixture to cellulose dyeing, also can dye under 130 ℃ the condition at the most in super-atmospheric pressure, temperature, also can use common dyeing auxiliaries, acid binding agent, can also use neutral salt and sodium-chlor or sodium sulfate, the product dyed thereby dye yield of dying in order to last method is very high, the fabulous and tonal match of color pile-on properties.A kind of feasible method is that filamentary material is placed warm dye bath, heats dye bath gradually, makes it reach required dyeing temperature, and finish dyeing course under this temperature.If desired, after also can reaching, in dye bath, add and to quicken the neutral salt that dyestuff dyes to the greatest extent at the dyeing temperature of reality.
The method of conventional printing cellulose fibres can produce the dark printing product of sharp outline and pure white ground colour too.This method can be undertaken by the one way mode, for example with the printing paste printing and dyeing that contain sodium bicarbonate or other acid binding agent and tinting material, 100-103 ℃ of following decatize; Or undertaken by the round trip mode, for example with the neutral or weakly acidic printing paste printing and dyeing that contain tinting material, then, the material of printing and dyeing is fixed by containing electrolytical thermokalite bath, fix after perhaps making its excessive tie dyeing with the tie dyeing liquid that contains alkaline electrolyte, thereafter, with the material after handling in batches or decatize or carry out dry heat treatment.The condition that changes fixed dye is very little to the influential effect of printing product printing and dyeing.Use dye mixture of the present invention, no matter be that dyeing or printing and dyeing can both reach very high degree of fixation.The warm air that conventional thermal fixing method is adopted in xeothermic fixedly operation, its temperature is 120-200 ℃.Except common 101-103 ℃ steam, also can use 160 ℃ superheated vapo(u)r and high compressed steam at the most.
Being used for the acid binding agent of dyestuff fixing on cellulosic fibre is the water-soluble alkaline salt of mineral acid or organic acid basic metal and alkaline-earth metal for example, and the compound that can discharge alkali during heating.Wherein, particularly suitable be alkali metal hydroxide and weak to moderate tart mineral acid or organic acid alkaline metal salt, preferred alkali metal compound is the compound of sodium and potassium.These acid binding agents are sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate, salt of wormwood, sodium formiate, SODIUM PHOSPHATE, MONOBASIC and Sodium phosphate dibasic.
Under heating or the condition that do not heat, handle the dyestuff of dye mixture of the present invention with acid binding agent, dyestuff chemistry is attached on the cellulosic fibre; Particularly, after the postprocessing working procedures of its flushing is removed loose dyestuff part, can demonstrate excellent wet fastness properties,, thereby be easy to it is washed out particularly because the solvability of loose dyestuff part in cold water is fine to cellulosic product dyed thereby.
The dyeing of urethane and tynex is normally carried out in acidic medium.Can contain for example acetic acid and/or ammonium sulfate and/or acetic acid and ammonium acetate or sodium-acetate in the dye bath, can make the pH of dye bath be adjusted to desirable value.In order to make dyeing reach acceptable level-dyeing property, it is desirable adding level dyeing auxiliary agent commonly used, for example based on the aniline sulfonic acid of cyanuryl chloride and three times of molar weights or the reaction product of napthylamine sulfonic acid, or based on the level dyeing auxiliary agent of the reaction product of for example stearylamine and oxyethane.Material that normally will be to be dyed places temperature to be about 40 ℃ dye bath, and it is stirred for some time, then, the pH of required weak acid (preferred weak acetic acid) is adjusted in this dye bath, and actual dyeing is to carry out under the temperature between 60-98 ℃.Yet, also can under boiling state or the highest 120 ℃ temperature (under super-atmospheric pressure), carry out.
Following examples will the invention will be further described.Except as otherwise noted, umber described in the literary composition and percentage number average are by weight.Parts by weight are similar to volume parts, as the corresponding liter of kilogram.
Embodiment 1
Contain ionogen dye powder (the navy blue dyeing disazo dyes that contains 50% structural formula (A)) with 200 parts
With 75 parts contain ionogen dye powder (the golden yellow dyeing monoazo-dyes that contains 70% structural formula (B))
Carry out mechanically mixing.Will be according to the present invention prepared dye mixture, when adopt present technique field fibre-reactive dyes commonly used use with fixing means the time, can on cellulosic fibre material for example, produce the product dyed thereby or the dyeing material of aterrimus tone.
Embodiment 2
Dye mixture of the present invention can be prepared as follows; with about 59 parts of yellow soda ash with 288 parts of 4-(β-sulfuric acid ethylsulfonyl) pH of the suspension of aniline and 250 parts of water is adjusted into 4.5-5; adding after 234 parts of (by volume) concentration are 30% aqueous hydrochloric acid and 400 parts of ice; with 143 parts of (by volume) concentration is that 38% sodium nitrate aqueous solution makes aniline compound diazotization; then; add 112 parts of 1-amino-8-naphthols-3; the 6-disulfonic acid; at pH is that 1-1.3(keeps this pH value with about 60 parts sodium bicarbonate); temperature is lower than carries out the coupled reaction first time under 20 ℃; add 57 parts of 2 hydroxy naphthalenes-6-carboxylic acid then; with yellow soda ash with pH regulator to 5-6, in 20 ℃ and this pH scope, carry out coupled reaction.
Reaction product is the dye solution of black, wherein contains structural formula described in the embodiment 1 (A) and dyestuff (B), and both ratios are 68.7%: 31.3%.
Add 5 parts of sodium phosphate buffer agents and the pH of this dye solution can be adjusted into 4.5.Water further dilutes or makes this solution evaporation, this liquid dye mixture gets final product stdn, thereby reaches the required concentration of liquid formulation, as usual, this liquid dye or can directly be used as dye bath or dye liquor also can or be used to prepare dye bath or dye liquor after adding an amount of alkaline reagents.This dye mixture can dye black product dyed thereby.
Embodiment 2a
The consumption that utilizes the method for embodiment 2 and change initial compounds can prepare similar dye mixture, for example uses 280 parts of 4-(β-sulfuric acid ethylsulfonyl) aniline, 102 parts of 1-amino-8-naphthols-3,6-disulfonic acid, 68 parts of 2 hydroxy naphthalene-6-carboxylic acids.Products therefrom is a kind of dye mixture, wherein structural formula (A) and (B) ratio of two kinds of dyestuff content be about 62.7%: 37.3%.This dye mixture can be separated it with for example spray-drying process from resulting solution, perhaps be directly used in dyeing as the liquid formulation with dissolved state as described in the embodiment 2.Adopt commonly used the using and fixing means in present technique field, can for example produce black product dyed thereby on the cellulosic fibre material equally.
Embodiment 3
Utilize novel dye mixture solution prepared among the embodiment 2 to be starting point, prepare a kind of dye mixture, wherein a part of dyestuff contains β-all the other dyestuffs of sulfuric acid ethylsulfonyl and then contains the ethene alkylsulfonyl.This kind solution separating is gone out 25%(by volume), adjust pH to 8 with yellow soda ash, then 20 ℃ of following restir 15 minutes, in this process, β-sulfuric acid ethylsulfonyl can change the ethene alkylsulfonyl into.After this, with sulfuric acid pH being harmonized is 4.5, and this ethene alkylsulfonyl dye mixture solution is added in original β-sulfuric acid ethylsulfonyl dye mixture.Products therefrom is a kind of structural formula (A-1) and aqueous dye solutions (B-1) of meeting.
Figure 931206006_IMG12
In the formula, 25% of Y is a vinyl, and 75% is β-sulfuric acid ethyl.
Additionally bring inorganic salt such as sodium sulfate in this aqueous dye solutions into by aforesaid method, can take that solution is cooled to 0 ℃ it is separated to a certain degree, then it is removed by filter.
With 5 parts of sodium phosphate buffer agents the pH of filtrate is adjusted into 4.5.Take to add the method for water or transpiring moisture, this aqueous dye solutions can be adjusted to the required concentration of liquid formulation, can be used for dyeing as embodiment 2 described methods.Adopt commonly used the using and fixing means of present technique field fibre-reactive dyes, can produce black product dyed thereby or dyeing material.
Embodiment 4
Dye mixture of the present invention can be prepared as follows; with about 20 parts of yellow soda ash with 118 parts of 4-(β-sulfuric acid ethylsulfonyl) pH of the suspension of aniline and 100 parts of water is adjusted into 4.5-5; then; stir for some time; adding after 100 parts of (by volume) concentration are 31% aqueous hydrochloric acid and 200 parts of ice, is that 38% sodium nitrite in aqueous solution makes aniline compound diazotization with 59 parts of (by volume) concentration.After diazotization reaction finishes, adds 134 parts of 1-amino-8-naphthols-3, the 6-disulfonic acid is lower than 20 ℃ in temperature, and maintenance pH carries out the coupled reaction first time under the condition of 1-1.3, then, saltouts with sodium-chlor the Monoazo compound of gained is separated.
The preparation method of another batch is; 261 parts of 2-methoxyl group-5-(β-sulfuric acid ethylsulfonyl) solution formed of aniline and 300 parts of water and 190 parts of (by volume) concentration are that aqueous hydrochloric acid and 300 parts of ice of 31% mix; then, be that 38% sodium nitrite in aqueous solution makes its diazotization with 117.5 parts of (by volume) concentration.Then, Monoazo compound and 79 parts of 2 hydroxy naphthalene-6-carboxylic acids of above gained are added in this diazonium salt solution, be about 20 ℃, keep pH to carry out coupled reaction under the condition of 5-6 in temperature.
The structural formula of gained (A) dyestuff and (C) the novel dye mixture solution of dyestuff
Figure 931206006_IMG13
Through spraying drying or with sodium-chlor saltout from resulting solution, separate after, can be directly routinely method be used for dyeing, or directly be used for dyeing with the dissolved solution state.In addition, adopt commonly used the using and fixing means of fibre-reactive dyes, can on cellulosic fibre material for example, produce the product dyed thereby of aterrimus tone.
Embodiment 5
Dye mixture of the present invention can be prepared as follows, adopts conventional method to prepare the disazo dyes of structural formula (A) and monoazo-dyes (D) in batches,
Then, two kinds of dye solutions are mixed by proper proportion, promptly can be made into the dye mixture aqueous solution of the present invention.
For example, by 292 parts of 4-(β-sulfuric acid ethylsulfonyl of diazotization) aniline, and with its diazonium salt and 159 parts of 1-amino-8-naphthols-3, the coupling of 6-disulfonic acid can make the disazo dyes of structural formula (A); With 162.6 parts of 2-methoxyl groups-5-methyl-4-(β-sulfuric acid ethylsulfonyl) aniline diazotization, then with 94 parts of 2 hydroxy naphthalenes-6-carboxylic acid coupling, can make the monoazo-dyes of structural formula (D), then, with these the two kinds dye solutions mixing that make.Adopt commonly used the using and fixing means of present technique field fibre-reactive dyes, this dye mixture can for example produce black product dyed thereby on the cotton products equally.
Embodiment 6
Contain ionogen dye powder and 20 parts that ionogen dye powder, 200 parts contain the navy blue look disazo dyes of 50% structural formula (A) that contain of 80 parts of tangerine look monoazo-dyes that contain 70% said structure formula (C) are mixed with machinery mutually for adjusting the ionogen dye powder that contains of coloured light with the yellow monoazo-dyes that contains 50% structural formula (E).
Figure 931206006_IMG15
Adopt commonly used the using and fixing means of present technique field fibre-reactive dyes, dye mixture of the present invention can produce the product dyed thereby and the dyeing material of aterrimus tone on cellulosic fibre material for example.
Embodiment 7
With 100 parts of golden yellow monoazo-dyes that contain 60% structural formula (F) contain the ionogen dye powder,
Figure 931206006_IMG16
（F）
Contain ionogen dye powder and 20 parts of 200 parts of navy blue look disazo dyess that contain 50% structural formula (A) carry out mechanically mixing for adjusting the ionogen dye powder that contains of coloured light with the red monoazo-dyes that contains 50% structural formula (G).
Figure 931206006_IMG17
Adopt commonly used the using and fixing means of present technique field fibre-reactive dyes, dye mixture of the present invention can produce the product dyed thereby and the dyeing material of aterrimus tone on cellulosic fibre material for example.
Embodiment 8
Repeat embodiment 2a with following initial compounds and consumption:
290 parts of 4-(β-sulfuric acid ethylsulfonyl) aniline, 102 parts of 1-amino-8-naphthols-3,6-disulfonic acid, 64 parts of 2 hydroxy naphthalene-6-carboxylic acids, and 17 parts of 1-Bian acyl amino-8-naphthols-3,6-disulfonic acid.
Products therefrom is a kind of dye mixture, cellulosic fibre material can be dyed to be the aterrimus tone.
Embodiment 9
With 72.4 parts of navy blue look disazo dyess that contain 50% structural formula (A) contain the ionogen dye powder and 27.54 parts of ionogen dye powders that contain that contain the golden yellow monoazo-dyes of 50% structural formula (B) carry out mechanically mixing.The dye mixture of gained according to the present invention, wherein, the ratio of structural formula (A) dyestuff and structural formula (B) dyestuff is 2.63: 1, adopt commonly used the using and fixing means of present technique field fibre-reactive dyes, dye mixture of the present invention can produce the product dyed thereby and the dyeing material of aterrimus tone on cellulosic fibre material for example.Its result not only color pile-on properties is good, and loose dyestuff partly is easy to wash out, and this dyeing can discharge.
Embodiment 10-40
Embodiment listed in the following table further illustrates the novel dye mixture that meets structural formula (10) and structural formula (11) with regard to the composition (definition of M is the same) of these dyestuffs.
Figure 931206006_IMG18
According to blending ratio of the present invention, when adopt present technique field fibre-reactive dyes commonly used use with fixing means the time, these dye mixtures can for example produce black product dyed thereby on the cellulosic fibre material.
Figure 931206006_IMG19
Figure 931206006_IMG20
Figure 931206006_IMG21
Figure 931206006_IMG22
Figure 931206006_IMG23
Figure 931206006_IMG24
Figure 931206006_IMG25
Figure 931206006_IMG26
Figure 931206006_IMG27

Claims (12)

1, a kind of dye mixture contains one or more disazo dyess that meet structural formula (1) and one or more meet the monoazo-dyes of structural formula (2),
Figure 931206006_IMG1
Wherein,
R 1, R 2, R 3, R 4, R 5And R 6Be respectively hydrogen, methyl, ethyl, methoxyl group, oxyethyl group, sulfonic group or carboxyl separately, can be mutually the same or different,
Y be respectively separately vinyl, β-chloroethyl, β-thiosulfuric acid ethyl or β-sulfuric acid ethyl and
M is hydrogen or basic metal,
This dye mixture comprises the disazo dyes that meets structural formula (1), and its content is 50-95% (by weight), and meets the monoazo-dyes of structural formula (2), and its content is 5-50% (by weight).
2, according to the dye mixture of claim 1, wherein one or more content that meet the disazo dyes of structural formula (1) be 60-80%(by weight), and one or more content that meet the monoazo-dyes of structural formula (2) be 40-20%(by weight).
3, according to the dye mixture of claim 1 or 2, R wherein 1, R 3And R 5Be respectively hydrogen or methoxyl group separately, R 2, R 4And R 6Respectively be hydrogen.
4, according to the dye mixture of claim 1 or 2, R wherein 1, R 2, R 3, R 4, R 5And R 6All respectively be hydrogen.
5, according at least one dye mixture among the claim 1-4, wherein, Y is respectively vinyl or β-sulfuric acid ethyl separately.
6, according to the dye mixture of claim 1, comprise that one or more disazo dyess that meet structural formula (10) and one or more meet the monoazo-dyes of structural formula (11),
Figure 931206006_IMG2
Figure 931206006_IMG3
Wherein, D 1, D 2And D 3Be respectively 3-vinyl sulfonyl-phenyl, 4-vinyl sulfonyl-phenyl, 3-(β-sulfuric acid ethyl sulphonyl separately) phenyl or 4-(β-sulfuric acid ethyl sulphonyl) phenyl, the definition of M is identical with the definition in the claim 1.
7, according to the dye mixture of claim 1, comprise that one or more disazo dyess that meet structural formula (10) and one or more meet the monoazo-dyes of structural formula (11),
Figure 931206006_IMG4
Wherein, D 1And D 2Be respectively 3-(β-sulfuric acid ethyl sulphonyl separately) phenyl, 4-(β-sulfuric acid ethyl sulphonyl) phenyl, 3-vinyl sulfonyl-phenyl or 4-vinyl sulfonyl-phenyl, and D 3Be 2-methoxyl group-5-(β-sulfuric acid ethyl sulphonyl) phenyl or 2-methoxyl group-5-vinyl sulfonyl-phenyl, the definition of M is identical with the definition in the claim 1.
8, according at least one dye mixture among the claim 1-7; wherein; this dyestuff exists with the mixture of ethene alkylsulfonyl and β-sulfuric acid ethylsulfonyl dyestuff, and the mol ratio of ethene alkylsulfonyl dyestuff and β-sulfuric acid ethylsulfonyl dyestuff is 5: 95-30: between 70.
9,, also comprise yellow or the red coloured light dyestuff of adjusting according at least one dye mixture among the claim 1-8.
10, a kind of aqueous solution preparation comprises as at least one dye mixture among the claim 1-9, wherein, the total content of dyestuff be 5-50%(by weight).
11, as at least one dye mixture or preparation among the claim 1-10, the application of dyeing and printing and dyeing on hydroxyl and/or formamyl filamentary material.
12, a kind of method that is used on hydroxyl and/or formamyl filamentary material dyeing and printing and dyeing; this method be by use a kind of dyestuff or dye mixture to this material and adopt the method for heating or by alkali or take not only to heat but by the method for alkali with dyestuff fixing on this material; this method comprises that using a kind of dyestuff, this dyestuff is at least one described dye mixture of item or preparation among the claim 1-10.
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